Method, system and device for reducing microbial concentration and/or biofilm formation and/or reducing mineral and chemical concentrations to purify contaminated surfaces and substances

ABSTRACT

Described herein are various methods, systems, and apparatus for reducing and eliminating, microbes, minerals, chemicals and biofilms from contaminated substances. A combination of oxidizing agents and radiation of certain wavelengths forming a synergistic reaction. The synergistic reaction generates EMODs, which are effective in reducing microbial count, unwanted mineral or chemical concentrations and eliminating or blocking biofilm formation, particularly in anaerobic environments. The synergistic reaction produces long lasting EMODs thereby creating a residual effect. This synergistic reaction has a relationship to EMOD creation and has a detrimental effect on microbial contamination (MC), mineral contamination (MINC), chemical contamination (CC), microbial influenced corrosion (MIC) and biofilm creation. MC, MINC, CC, MIC and biofilm can be eliminated or greatly reduced with the treatment methods in or on equipment including pipelines, storage tanks, supplying systems, cooling systems, and processing equipment.

BACKGROUND

The phenomena of microbiological contamination, mineral contamination,chemical contamination and biofilm formation in crude oil, natural gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substances and surfaces represent a broad problem.Microbial contamination (MC), mineral contamination (MINC), chemicalcontamination (CC) and microbial influenced corrosion (MIC) all posesevere operational, environmental, and safety problems to the variousindustries related to petroleum, natural gas, water, wastewater,production fluids, soil and air or other contaminated substances,particularly with respect to degradation of the substances and corrosivedamage of equipment used in the storage, processing, and/or transport ofraw materials and/or processed products, including but not limited tohydrocarbon substances such as crude, oil and gas, dairy products, foodproducts, water, wastewater, production fluids, soil, air and othercontaminated substances.

First, the degradation of petroleum hydrocarbons, water, wastewater,production fluids, soil, air and other contaminated substances isassociated with the negative effect of microorganisms. The microbes usematerial contained in these substances as a source of “food” and changethe properties of these substances, thus reducing its value. Forexample, the changes in oil density, sulfur content and viscosity causedisruption in oil extraction and processing technology, bring aboutsignificant economic losses and cause adverse environmental effects.Industry research indicates that 10%-14% of oil and gas is lost due tomicrobial contamination.

Also, problems influence the ways petroleum hydrocarbons, water,wastewater, production fluids, soil, air and other contaminatedsubstances are stored, transported and processed. The adverse activityof microorganisms causes corrosion of transmission installations (e.g.,pipelines of oil, gas, water and wastewater), producing undesirablesubstances (e.g., H₂S, polymers, organic acids, etc.) that affect theperformance and/or quality of the transported substances. Costsresulting from MC, MINC, CC and MIC and biofilm formation in theseindustries occur due to repair and replacement of damaged equipment,spoilage, environmental clean-up, and injury-related health care, amountto well over several tens of billions of USDs per year. Unwanted mineralconcentrations in hydrocarbons and produced water can be divided intotwo main areas, Sulfur and Iron. Sulfur content of crude oils is one ofthe most important properties relating to crude oils. Sulfur content isexpressed as weight percent of sulfur in oil and typically varies in therange from 0.1 to 5.0% wt. The standard methods that are used to measurethe sulfur content are ASTM D129, D1552, and D2622, depending on thesulfur level. Crude oils with more than 0.5% wt sulfur need to betreated extensively during petroleum refining. Using the sulfur content,crude oils can be classified as sweet (<0.5% wt S) and sour (>0.5% % wtS). The distillation process segregates sulfur species in higherconcentrations into the higher-boiling fractions and distillationresidual. Removing sulfur from petroleum products is one of the mostimportant processes in a refinery to produce fuels compliant withenvironmental regulations. The typical concentration of iron (II)produced water that results from the fracking process is in the range of25 to 55 mg/L

The maximum permissible limit for iron (H) in production water that isto be reused or disposed of is 0.5 mg/L, beyond which causes operationalissues including pipeline blocking, plugging of formations, corrosion ofthe metallic parts, and increased turbidity of effluent stream, leadingto higher production costs. Even at low concentrations, iron (II) indrinking water can affect aesthetics and other quality such as bad tasteand color, staining, and deposition in the water leading to highturbidity. Reusing or disposing of produced water requires mineralcontents to be reduced in most instances.

A variety of strategies have been developed to mitigate the negativeeffects of MC, MINC, CC, MIC and/or the biofilms that contribute orcause MC, MINC, CC and MIC. Such techniques include the use of corrosionresistant metals, oxidizing agents, temperature control, pH control,radiation, filtration, protective coatings with corrosion inhibitors,chemical controls (e.g., biocides, oxidizers, acids, alkalis),bacteriological controls (e.g., phages, enzymes, parasitic bacteria,antibodies, competitive microflora), pigging (i.e., mechanicaldelamination of corrosion products), anodic and cathodic protection, andmodulation of nutrient levels. Attempts to eliminate microorganismstypically involve using chemicals exhibiting biocidal properties, whichbesides the physical methods is the most popular and most effectivetechnique of eliminating microbiological contamination, microbiologicalinfluenced corrosion and biofilm formation. Attempts to eliminateunwanted mineral concentrations typically involve using chemicalsexhibiting biocidal properties, flocculants, and precipitants whichbesides the physical methods are the most popular and most effectivetechnique of eliminating unwanted mineral concentrations. However, theselection of appropriate flocculants, precipitants, antimicrobial orantifungal agents requires the consideration of factors affecting theefficiency of the process. In fact, each of these existing methods faceobstacles, such as, high cost, lack of effectiveness, short life-span,or requirement for repeat applications. For example, regular biocideinjections are only effective sometimes and only in particularenvironments. In addition, biocides often fail due to incompatibilitywith other commonly used corrosion inhibitors and because of biofilmpermeability issues, i.e., the biocides are unable to penetrate orpermeate the biofilms due to the properties of the extracellular matrixof the biofilms. In addition, many of the above controls are notpractical for implementing in many instances due to the potential effecton the downstream processes.

In industry, undesired minerals and chemicals in solution contribute toeconomic and environmental loss. In the petroleum industry, waterproduced with hydrocarbons is commonly contaminated with chemicalsand/or minerals. Produced water is disposed of in a variety of ways thatinclude reuse, evaporation and injection in disposal wells. Mineral andchemical contaminants, in many cases, need to be reduced or eliminatedprior to disposal methods to prevent adverse effects such as groundwater contamination, soil contamination and underground water reservoircontamination. Produced water with unwanted high mineral content canalso adversely affect underground oil and gas formations by occludingthe producing formations.

In pipelines, pigging and biocides are the most commonly used approachesfor controlling biofilms and corrosion. Pigging is required to remove ordisrupt the biofilm on the pipe surfaces. Pigging can also remove manyof the harmful iron sulfide deposits. While pigging will besubstantially effective where thick biofilms are present, thin biofilmsand thin iron sulfide deposits are not appreciably affected by thescraping action of pigs. Subsequently, biocides and storage systems.However, biocides are not typically effective in penetrating thebiofilms, and therefore, have reduced effectiveness against theunderlying bacteria. Combination treatments in conjunction with piggingare more effective than the chemical treatments alone. However,treatments must be made routinely on a fixed schedule or else thebacteria population increases significantly, and control becomes evenmore difficult.

Thus, there exists a need in the art for an improved approach forinhibiting and reducing microbial concentration, mineral concentration,chemical concentrations, and/or biofilm formation that avoids the aboveindicated problems associated with existing methods, and in particular,which effectively reduces, mitigates, or otherwise eliminates microbialcontamination, mineral contamination, chemical contamination, microbialinfluenced corrosion and/or associated biofilms in/on equipment used tostore, transport and/or process crude, oil, gas, hydrocarbons, water,wastewater, food, dairy products, production fluids, soil, air and othercontaminated substances.

SUMMARY

Various methods, systems and devices for reducing microbialconcentration, mineral concentrations, and chemical concentrations incrude, oil, gas, hydrocarbons, water, wastewater, frack water, producedwater from petroleum industry processes, production fluids, soil, food,produce, animals, air and other contaminated substances or for reducingbiofilms formed in the substances, on the surface of the substances, oron the surface of equipment involved in the storage, transport orprocessing of the substances may be shown and described herein. Themethods, systems and devices may find application in the oil and/ornatural gas production industries, antimicrobial applications, coolingand processing systems of water, decolonization, Fenton's reagent andhydrogen peroxide applications, filamentous bulking controlapplications, gas scrubbing applications, sulfide oxidationapplications, peracetic acid disinfectant application, fracking waterdecontamination applications, mineral and chemical reductionapplications, precipitation applications, etc. More particularly, themethods, systems and devices may be used for mitigating or eliminatingmicrobial contamination (MC), mineral contamination (MINC), and chemicalcontamination (CC) in crude, oil, gas, hydrocarbons, water, wastewater,production fluids, soil, food, produce, animals, air and othercontaminated substances, microbial influenced corrosion (MIC) on metalsurfaces, and/or creation and activity of biofilms in these substances.

Exemplary embodiments relate, in part, to a discovery that oxidizingchemicals, together with radiation of certain wavelengths, form asynergistic reaction generating electrically modified oxygen derivatives(EMODs). These EMODs may consist of Reactive Oxygen Species (ROS) andReactive Nitrogen Species (RNS). The radiation is dosed to create thissynergistic reaction with the oxidizing agent. The Physics' definitionof “radiation dose” refers to absorbed radiation, and exposure to theincident radiation. Quite frequently dose is used in the biologicalliterature when referring to exposure. Both dose and exposure arequantities integrated over time, they are not rates. The rate quantitycorresponding to exposure is irradiance. All these quantities describeradiation as measured on a plane (or flat surface) and are expressed perunit area. Another name for irradiance is ‘vector irradiance’.

Light fluence rate gives the radiation incident on a sphere of unitcross section and is expressed per unit surface area (of the sphere) andper unit time. The corresponding time integrated quantity is lightfluence. Another name for fluence rate is ‘scalar irradiance’. Fluencerate and (vector) irradiance are expressed in the same units, but theyare different quantities.

In addition, this newly discovered synergistic reaction produces EMODsthat exist for a prolonged period of time and in greater numbers thanpreviously recorded. The reaction generates EMODs. A percentage of theseEMODs are available to perform antimicrobial activities. A percentage ofthese EMODs are available to reduce mineral concentrations. A percentageof these EMODs are available to generate additional EMODs. The reductionof oxygen through the addition of electrons leads to the formation of anumber of EMODs including: superoxide; hydrogen peroxide; hydroxylradical; hydroxyl ion; and nitric oxide. The rate of production of EMODsis dependent on the dose of radiation. The EMOD known as a hydroxylradical has a very short in vivo half-life of approximately 10⁻⁹ secondsin a biologic system and a high reactivity. In an environmental systemwhere antioxidants don't exist, or they exist in small numbers thehydroxyl radicals can exist for minutes. The EMOD known as the hydroxylion is a negatively charged molecule consisting of one oxygen atombonded to one hydrogen atom. When dissolved in water, the hydroxyl ionis an incredibly strong base. In fact, according to the Arrheniusdefinition of a base, the presence of a hydroxyl ion is what makes achemical a base. The hydroxyl ion has been demonstrated to exist forover 1 hour. The EMOD known as singlet oxygen exists where the energydifference of 94.3 kJ/mol between ground state and singlet oxygencorresponds to a forbidden singlet-triplet transition in thenear-infrared at ˜1270 nm. As a consequence, singlet oxygen in the gasphase is extremely long lived 72 minutes or longer. Our recentlydiscovered process produces EMODs that exist for seconds, minutes, hoursand days longer than previously reported. This discovery allows for anoxidizing agent to be exposed to certain wavelengths of radiation and ata dose that is deemed appropriate creating a synergistic effect whichproduces EMODs that may be available for later use due to the createdEMODs long lasting existence. This long-lasting existence can bereferred to as a residual effect. Prior to the disclosure, thissynergistic reaction involving oxidizing agents and radiation of certainwavelengths was not known or appreciated as to its connection with EMODcreation or its effects on elimination or mitigation of MC, MINC, CC,MIC or biofilm creation.

The resultant synergistic reaction may significantly reduce microbialconcentration, mineral concentrations, chemical concentrations andbiofilms on surfaces and in solutions, and, consequently, may be used toreduce, mitigate, or eliminate microbial contamination (MC), mineralcontamination (MINC), chemical contaminations (CC) in crude, oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substances and/or microbial influenced corrosion (MIC) onmetal surfaces, in particular, metal surfaces of equipment involved inthe storage, transport, and processing of these substances. Experimentshave demonstrated that the combined synergistic reaction is over 300percent more effective in elimination of MC, MINC, CC, MIC and/orbiofilm formation than either the oxidizing chemicals or the radiationif acting individually. Additionally, generated EMODs are available fora period of time that has previously not been recorded. Research hasshown the previously expected EMOD lifespan can now be greatly extendedto seconds, minutes, hours, and days. Two of the toughest challengesfacing water treatment today are effective iron and hydrogen sulfideremoval. As an example, ferrous iron (Fe+2), often occurs naturally ingroundwater sources, and can also be found in industrial process andwastewaters, e.g. oil field produced water, steel mills & coal mines(acid mine drainage).

Oxidizing agents can be used to quickly oxidize soluble ferrous iron toferric (Fe+3), forming a rapidly settling ferric hydroxide floc. Theresulting floc can be removed with filtering or a clarifier. An exampleof this reaction is shown below:

2Fe+2+H2O2+4OH—→2Fe(OH)3(precip.)

Hydroxyl radicals bind to ferrous iron to form ferric iron that willprecipitate out of a solution. The rate of precipitation is dependent ona number of factors chief of which is the availability of hydroxylradicals. The described method of using an oxidizing agent in asynergistic reaction with radiation of certain wavelengths in generatingan increased number of hydroxyl radicals that are available for longerperiods of time than have previously been reported creates a mineralprecipitation rate greater than previously available for a givenconcentration of the oxidizing agent. This provides a cost savings toindustry, lessens negative environmental impacts associated with mineralcontamination and also provides health benefits created by the removalof unwanted mineral contaminations.

In one aspect, a method for reducing microbial concentration, mineralcontamination, and chemical contamination in crude oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substances or for reducing biofilms formed in thesubstances, on the surface of the substances, or on the surface ofequipment involved in the storage, transport or processing of thesubstances may be provided. The method may include introducing aneffective amount of a composition having an oxidizing agent compoundinto the substances to be treated and then exposing the resulted mixtureof the substances and the composition to radiation of certainwavelengths. The method may include introducing an effective amount of acomposition having an oxidizing agent compound while exposing theoxidizing agent to radiation of certain wavelengths as it is introducedinto a target substance. The method may include exposing an effectiveamount of an oxidizing agent compound to radiation of a certainwavelength before it is introduced to a target. The compositioncomprising the oxidizing agent compound may function together with theradiation of certain wavelengths to lead to a synergistic reactioncreating EMODs that exist for a previously undiscovered, longer periodof time and in greater quantities than expected from traditional uses ofoxidizing agents thereby reducing or eliminating microbes, minerals,chemicals and the biofilm and/or sludge that is associated with them.

In another aspect, a combination for reducing microbial concentration,mineral concentration, and chemical concentration in crude oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substances or for reducing biofilms formed in thesubstances, on the surface of the substances, or on the surface ofequipment involved in the storage, transport or processing of thesubstances may be provided. The combination may include a compositionhaving an oxidizing agent compound and radiation of certain wavelengths.The composition including the oxidizing agent compound may functiontogether with the radiation of certain wavelengths to lead to asynergistic reaction creating EMODs that exist for an extended period oftime. Previous reports have explained an expected existence of EMODS inbiologic systems in nanoseconds. Our newly discovered technologycentered on the synergistic reaction between an oxidizing agent andcertain wavelengths of radiation demonstrate an EMOD existence measuredin seconds, minutes, hours and days. These long lasting EMODs reduce oreliminate unwanted concentrations of microbes, minerals, chemicals andthe biofilm and/or sludge that they produce.

In still another aspect, a device for reducing microbial concentration,mineral concentrations, and chemical concentrations in crude oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substances or for reducing biofilms formed in thesubstances, on the surface of the substances, or on the surface ofequipment involved in the storage, transport or processing of thesubstances may be provided. The device may include an oxidizing agentintroducing component and a radiation emitting component. The oxidizingagent introducing component may be adapted to introduce a composition ofan oxidizing agent compound to the hydrocarbon, produced water, frackwater, ground water, gas or other targets to be treated. The oxidizingagent introducing component of the device may be, for example, atitration system. The radiation emitting component may be adapted toemit or create radiation of certain wavelengths. The radiation may beapplied to the oxidizing agent before, during or after the oxidizingagent is applied to a target. The composition comprising the oxidizingagent compound may function together with the radiation of certainwavelengths to lead to a synergistic reaction creating EMODs that existfor seconds, minutes, hours or days, thereby reducing or eliminatingunwanted microbes, minerals, chemicals and the contaminants, biofilmsand/or sludge that they produce.

In certain embodiments, the radiation of certain wavelengths may beradiation of a wavelength between 200 nanometers and 700 nanometers,such as from 300 nanometers to 600 nanometers, or from 400 nanometers to500 nanometers.

In certain embodiments, the effective amount of the oxidizing agentcomposition may provide the minimal amount of the oxidizing agentcompound which results in a measurable or detectable effect on theunwanted microbial, mineral, and/or chemical concentrations or thebiofilm formation.

In certain embodiments, the effective amount of the oxidizing agentcomposition may provide a concentration of the oxidizing agent compoundthat is from 0.0001 percent to 100 percent or greater, such as from0.001 percent to 0.3 percent or from 3 percent to 50 percent or greaterthan 100 percent. of the volume of the substance to be treated. Forexample, from Higher levels of contamination will require a higher levelof an oxidizing agent component to reduce the contaminant level. Incases of the contamination level is so high that it is necessary to useconcentrations of oxidizing agents that are greater than the volume ofthe substance containing the contaminants. Low levels of microbialcontamination, mineral contamination, microbial influenced corrosion,and biofilm contamination may be reduced with oxidizing agentconcentrations as low as 1 part per million.

In certain embodiments, the effective amount of the compositioncomprising the oxidizing agent may be determined on the basis of any oneor more of the density, pH, temperature, viscosity and light absorbingquality of the substance to be treated, and the size and shape of thecontainer thereof. For example, oil has a density and viscosity thatimpede the penetration of an oxidizing agent, whereas clean water wouldnot. Moreover, iron precipitates out of solution better in a basicenvironment, than an acidic one. Further, increasing the temperature mayincrease the desired reaction rate.

In certain embodiments, the oxidizing agent compound may be hydrogenperoxide, hypochlorous acid, chlorine, peracetic acid, urea, carbamideperoxide, or benzoyl peroxide or any other suitable oxidizing agent.

In certain embodiments, the formulation of the oxidizing agentcomposition may be determined on the basis of whether the substance tobe treated is under aerobic or anaerobic conditions, pH of thesubstance, mineral content of the target, chemical content of the targetsalinity of the substance, consortium or population characteristics ofthe microorganism present in the substance, the microbial content of thesubstance and/or the microbial content of the biofilms. For example, theformulation may need to be modified for higher mineral and/or chemicalcontents, which may impede the penetration of an oxidizing agent, andfor an iron content, for example, a formulation with a basic pH isbetter for removal.

In certain embodiments, the composition comprising the oxidizing agentcompound may further include at least one other inhibitor againstmicrobial, mineral or chemical contamination in crude, oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substances and/or microbial influenced corrosion on a metalsurface.

In certain embodiments, the at least one other inhibitor may be abiocide selected from a group of germicides, antibiotics,antibacterials, antivirals, antifungals, antiprotozoals andantiparasites.

In certain embodiments, the wavelength, intensity, duration time and/orlocation relative to the hydrocarbon to be treated, of the radiation,may be determined on the basis of any one or more of the density andlight absorbing quality of the crude, oil, gas, hydrocarbons, water,wastewater, production fluids, soil, air and other contaminatedsubstances, the size and shape of the container thereof, whether thesubstance to be treated is under aerobic or anaerobic conditions, pH ofthe substance, mineral content of the target, chemical content of thetarget, temperature of the target, salinity of the substance, consortiumor population characteristics of the microorganism present in thesubstance, and the microbial content of the biofilms. For example,higher mineral and/or chemical contents may require different radiationtreatment than lower contents, as the mineral and/or chemical contentsmay impede the penetration radiation.

In certain embodiments, a secondary treatment may be carried out forreducing unwanted microbial mineral and chemical concentrations orbiofilm formation, which may be selected from the group consisting ofpigging, sonication, radiation, filtration, stirring, bacteriologicalcontrol, chemical control, temperature control, pH adjustment, nutrientadjustment, anodic and cathodic protection, protective coating withcorrosion inhibitors, and installation of corrosion resistant metals.

In certain embodiments, the unwanted microbial, mineral or chemicalconcentration or the biofilms may be associated with fungi.

In certain embodiments, the unwanted microbial, mineral, and chemicalconcentrations or the biofilms may be associated with aerobic bacteria.

In certain embodiments, the unwanted microbial, mineral or chemicalconcentrations or the biofilms may be associated with anaerobicbacteria.

In certain embodiments, the anaerobic bacteria may be selected from thegroup of sulfate-reducing bacteria, iron-oxidizing bacteria,sulfur-oxidizing bacteria, nitrate reducing bacteria, methanogens, andacid producing bacteria. The sulfate-reducing bacteria may be of thegenera Desulfovibrio, Desulfotomaculum, Desulfosporomusa,Desulfosporosinus, Desulfobacter, Desulfobacterium, Desulfobacula,Desulfobotulus, Desulfocella, Desulfococcus, Desulfofaba, Desulfofrigus,Desulfonema, Desulfosarcina, Desulfospira, Desulfotalea, Desulfotignum,Desulfobulbus, Desulfocapsa, Desulfofustis, Desulforhopalis,Desulfoarculus, Desulfobacca, Desulfomonile, Desulfotigmum,Desulfohalobium, Desulfomonas, Desulfonatronovibrio, Desulfomicrobium,Desulfonatronum, Desulfacinum, Desulforhabdus, Syntrophobacter,Syntrophothermus, Thermaerobacter, and Thermodesulforhabdus.

In certain embodiments, the susceptible metal surface may be a metalsurface of equipment for storing, transporting or processing of oil,gas, water, wastewater, production fluids, soil, air and othercontaminated substances. Such equipment may be, for example, metal(e.g., steel) pipelines, storage containers, refinery processingequipment and other processing equipment.

In certain embodiments, the oxidizing agent composition including theoxidizing agent compound may be an aqueous composition.

In certain embodiments, the oxidizing agent composition including theoxidizing agent compound may be a non-aqueous composition.

In certain embodiments, the oxidizing agent composition including theoxidizing agent compound may have an acidic pH, ranging from about6.0-7.0, to about 5.5-6.5, to about 4.5-5.5, to about 3.5-4.5, to about2.5-3.5, to about 1.5-2.5, or lower than 1.5.

In other embodiments, the oxidizing agent composition including theoxidizing agent compound may have a basic pH, ranging from about7.0-7.5, to about 7.5-8.5, to about 8.5-9.5, to about 9.5-10.5, to about10.5-11.5, to about 11.5-12.5, to about 12.5-13.5 to about 14.

In still other embodiments, the oxidizing agent composition includingthe oxidizing agent compound may have a neutral pH, ranging from about6-8, or about 6.5-7.5, or about 6.7-7.3, or about 6.8-7.2, or about6.9-7.1, or about 7.

In still other embodiments, the pH of the environment of or surroundingthe substance to be treated and/or its derivatives to be treated may beadjusted with buffers or other pH-altering agents to adjust the pH toany basic, neutral, or acidic conditions.

In certain embodiments, the effective amount of the oxidizing agentcomposition may be from 3% to 50% weight of the composition, such asdepending on viscosity, temperature, density, pH, etc. comprising theoxidizing agent compound may be deposited in the water that exists wherethe substance to be treated is collected, stored or transported.Recognizing that the microbes require water to survive and multiply,treating the water with the oxidizing agent that has been exposed toradiation, or is exposed to radiation while it is applied or is exposedto radiation after it is applied to a target may create EMODs thatreduce or eliminate the MC, MINC, CC, MIC and/or biofilm.

The exemplary methodologies shown and described herein can providenumerous advantageous over existing mitigation practices, such as, butnot limited to:

(a) By generating a greater amount of EMODs utilizing the synergisticreaction between an oxidizing agent and certain wavelengths ofradiation, reduced quantities of the oxidizing agent may be needed thanused in more traditional methods.

(b) By generating longer lasting EMODs utilizing the synergisticreaction between an oxidizing agent and certain wavelengths ofradiation, reduced quantities of the oxidizing agent may be needed thanused in more traditional methods.

(c) the oxidizing agent may be a natural product of environmentalbacteria, hence minimal environmental impact compared to currentlyavailable biocides;

(d) in existing methods, biocides are naturally taken up by bacteria ina biofilm and induce a switch to planktonic growth behavior (i.e.,growth away from biofilm environment) and thus, lack biofilmpermeability aspects needed to better eliminate MC, MINC, CC and MIC;

(e) this MC, MINC, CC and MIC eliminating or reducing treatment may becompatible with commercial corrosion inhibitors, whereas many currentbiocides are not;

(f) the synergistic reaction between the oxidizing agent and theradiation which produces EMODs presents no negative environmentalimpact, which is unique compared with current methods of treating MC,MNC, CC and MIC, and thus this invention results in a more completeelimination or reduction in MC, MINC, CC and MIC than currentlyavailable methods; and

(g) the reduction in MC, MINC, CC and MIC by the method disclosed in theinvention is significantly greater than that by currently availablemethods when using similar concentrations of oxidizing agents.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of exemplary embodiments of the method, combination anddevice for reducing unwanted microbial, mineral and chemicalconcentrations or biofilm formation will be apparent from the followingdetailed description of the exemplary embodiments. The followingdetailed description should be considered in conjunction with theaccompanying figures in which:

FIG. 1 depicts a diagram showing an exemplary embodiment in which amethod is applied in a storage tank of crude oil, gas, hydrocarbons,water, wastewater, production fluids, air or other contaminatedsubstance which have less density than water;

FIG. 2 depicts a diagram showing an exemplary embodiment in which amethod is applied in a storage tank of crude oil, gas, hydrocarbons,water, wastewater, production fluids, air or other contaminatedsubstance which have greater density than water;

FIG. 3 depicts a diagram showing an exemplary embodiment in which amethod is applied in a length of pipeline of crude oil, gas,hydrocarbons, water, wastewater, production fluids, air or othercontaminated substance;

FIG. 4 depicts a diagram showing an exemplary embodiment in which amethod is applied where crude oil, gas, hydrocarbons, water, wastewater,production fluids, air or another contaminated substance is passedthrough a series of treatment areas;

FIG. 5 depicts a diagram showing an exemplary embodiment in which themethod is applied in the form of a closed loop system fordecontaminating a substance to be treated; and

FIG. 6 depicts a diagram showing exemplary an embodiment in which themethod is applied in the form of an open loop system for decontaminatinga substance to be treated.

FIG. 7 depicts an oxidizing agent titration system where the oxidizingagent is exposed to certain wavelengths of radiation before theoxidizing agent is applied to a target.

DETAILED DESCRIPTION

Aspects of the present invention are disclosed in the following detaileddescription and related figures directed to specific exemplaryembodiments of the invention. Those skilled in the art will recognizethat alternative exemplary embodiments may be devised without departingfrom the spirit or the scope of the claims. Additionally, well-knownelements of exemplary embodiments of the invention will not be describedin detail or will be omitted so as not to obscure the relevant detailsof the invention.

As used herein, the word “exemplary” means “serving as an example,instance or illustration.” The embodiments described herein are notlimiting, but rather are exemplary only. It should be understood thatthe described embodiments are not necessarily to be construed aspreferred or advantageous over other embodiments. Moreover, the terms“embodiments of the invention”, “embodiments” or “invention” do notrequire that all embodiments of the invention include the discussedfeature, advantage, or mode of operation.

Unless defined otherwise, all technical and scientific terms used hereinhave the meaning commonly understood by a person skilled in the art towhich this disclosure belongs. The following terms may have meaningsascribed to them below, unless specified expressly otherwise. However,it should be understood that other meanings that are known or understoodby those having ordinary skills in the art are also possible, and withinthe scope of the present disclosure.

As used herein, the term “biocide” refers to a chemical substance ormicroorganism which can deter, render harmless, or exert a controllingeffect on any harmful organism by chemical or biological means. Biocidesinclude not just those that are synthetic, but also those that arenaturally obtained, e.g., obtained or derived from bacteria and plants.Biocides can include, but are not limited to, germicides, antibiotics,antibacterials, antivirals, antifungals, antiprotozoals andantiparasites. Such compounds that can be used as biocides are wellknown in the art and may be obtained easily from commercial sources.

As used herein, the terms “microbial contamination” (or “MC”), “mineralcontamination” (MINC), “chemical contamination” (CC) and “microbialinfluenced corrosion” (or “MIC”), or similar terms, are well known termsin the art and shall be understood according to the meaning ascribed inthe field. In other words, MC, MINC, CC and MIC mean contamination ofcrude oil, gas, hydrocarbons, water, wastewater, production fluids,soil, air and other contaminated substances and corrosion to metalsurfaces caused directly or indirectly through the effects of bacteria,minerals, chemicals and their byproducts and metabolites, includingespecially bacteria that grow on the metal surface in a biofilm. MC andMIC can occur in both aerobic and anaerobic conditions and generally arethought to at least require the presence of bacteria in a biofilm. MC isconsidered “biotic contamination.” MIC is considered “biotic corrosion.”MC, MINC and CC are also associated with sludge formation in crude, oil,gas, hydrocarbons, wastewater, soil, air and other contaminatedsubstances resulting from the growth of microbes therein or in the waterassociated therewith. MIC, MINC and CC are also associated with surfacepitting, which leads to more rapid corrosive failure than uniformcorrosion.

As used herein, the term “corrosion associated biofilms” refers tobiofilms that have corrosive properties which contribute to microbialinfluenced corrosion.

As used herein, the term “corrosion” refers to the general deteriorationof a material (e.g., metallic material) due to its reaction with theenvironment.

As used herein, the term “oxidizing agent” refers in chemistry to asubstance that has the ability to oxidize other substances—in otherwords to cause them to lose electrons. Typical oxidizing agents includeoxygen, hydrogen peroxide, hypochlorous acid, chlorine, urea and thehalogens. In one sense, an oxidizing agent is a chemical species thatundergoes a chemical reaction that removes one or more electrons fromanother atom. In that sense, it is one component in anoxidation-reduction (redox) reaction. In the second sense, an oxidizingagent is a chemical species that transfers electronegative atoms,usually oxygen, to a substrate.

As used herein, “oxidizing agent equivalent” or “oxidizing analog orfunctionally equivalent compound, molecule or derivative” or similarterms include any known or yet unknown compounds that have a structurethat is similar to oxidizing agents to a degree such that they canproduce the same or similar biological effects as oxidizing agents.

Common oxidizing agents (O-atom transfer agents) may include, but arenot limited to: (1) oxygen (O₂), (2) ozone (O₃), (3) hydrogen peroxide(H₂O₂) and other inorganic peroxides, Fenton's reagent, (4) fluorine(F₂), chlorine (Cl₂) and other halogens, (5) nitric acid (HNO₃) andnitrate compounds, (6) sulfuric acid (H₂SO₄), (7) peroxydisulfuric acid(H₂S₂O₈), (8) peroxymonosulfuric acid (H₂SO₅), (9) chlorite, chlorate,perchlorate, and other analogous halogen compounds, (10) hypochloriteand other hypohalite compounds, including household bleach (NaClO), (11)hexavalent chromium compounds such as chromic and dichromic acids andchromium trioxide, pyridinium chlorochromate (PCC), andchromate/dichromate compounds, (12) permanganate compounds such aspotassium permanganate, (13) sodium perborate, (14) nitrous oxide (N₂O),nitrogen dioxide (NO₂), dinitrogen tetroxide (N₂O₄), (15) potassiumnitrate (KNO₃), the oxidizer in black powder, (16) sodium bismuthate,(17) peracetic acid and (18) urea.

As used herein, the term “radiation” refers in physics to the emissionor transmission of energy in the form of waves or particles throughspace or through a material medium. This includes, but is not limitedto: (1) electromagnetic radiation, such as radio waves, microwaves,ultraviolet light, visible light, x-rays, and gamma (γ) radiation, (2)particle radiation, such as alpha (α) radiation, beta (β) radiation, andneutron radiation (particles of non-zero rest energy), (3) acousticradiation, such as ultrasound, sound, and seismic waves (dependent on aphysical transmission medium), and (4) gravitational radiation,radiation that takes the form of gravitational waves, or ripples in thecurvature of spacetime.

The word “radiation” arises from the phenomenon of waves radiating(i.e., traveling outward in all directions) from a source. This aspectleads to a system of measurements and physical units that are applicableto all types of radiation. Because such radiation expands as it passesthrough space, and as its energy is conserved (in vacuum), the intensityof all types of radiation from a point source follows an inverse-squarelaw in relation to the distance from its source. Like any ideal law, theinverse-square law approximates a measured radiation intensity to theextent that the source approximates a geometric point. Some of theultraviolet spectrum that begins above energies of 3.1 eV, a wavelengthless than 400 nm is non-ionizing, but is still biologically hazardousdue to the ability of single photons of this energy to cause electronicexcitation in biological molecules, and thus damage them by means ofcertain reactions. This property gives the ultraviolet spectrum some ofthe properties of ionizing radiation in biological systems withoutactual ionization occurring. In contrast, visible light andlonger-wavelength electromagnetic radiation, such as infrared,microwaves, and radio waves, consists of photons with too little energyto cause damaging molecular excitation. Light, or visible light, is avery narrow range of electromagnetic radiation of a wavelength that isvisible to the human eye, or 380-750 nm which equates to a frequencyrange of 790 to 400 THz respectively. More broadly, physicists use theterm “light” to mean electromagnetic radiation of all wavelengths,whether visible or not.

As used herein, the term “sulfate-reducing bacteria” or “SRB,” which areconsidered one of the main culprits of biotic contamination and bioticcorrosion in anaerobic conditions, are a grouping of bacteria thatincludes at least 220 species which produce H₂S and use sulfates as theterminal electron acceptor. Most SRB are considered obligate anaerobes,meaning that the cells cannot metabolize and/or replicate in thepresence of oxygen, although many species can temporarily tolerate lowlevels of oxygen. Furthermore, anaerobic conditions capable ofsupporting SRB growth can be created in overall aerobic environments,due to the micro-niches created within the bacterial biofilm/corrosionproduct layer. Although SRB are the most studied and well understood ofthe anaerobic corrosion inducing bacteria, both MC and MIC can occur inanaerobic conditions in the absence of SRB.

As used herein, the term “pigging” refers to a well-known process ofintentional mechanical delaminating corrosion products and/or biofilmmaterial from metal surfaces.

As used herein, the singular forms “a”, “an”, and “the” include pluralreferences unless the context clearly dictates otherwise. All numericalvalues within the detailed descriptions and the claims herein aremodified by “about” or “approximately” the indicated value and take intoaccount experimental error and variations that would be expected by aperson having ordinary skills in the art.

Reference will now be made in detail to exemplary embodiments of thedisclosure. In certain exemplary embodiments, and generally referring toFIGS. 1-3, a system, device and method of reducing microbial, mineraland chemical concentrations in crude oil gas, hydrocarbons, water,wastewater, production fluids, soil, air and other contaminatedsubstance or for reducing biofilms formed in the substance, on thesurface of the substance, or on the surface of equipment involved in thestorage, transport or processing of the substance may be shown anddescribed. It will be appreciated that this disclosure provides aneffective and cost-efficient solution to solve the problem of microbialcontamination (MC), mineral contamination (MINC), and/or chemicalcontamination (CC) in a composition comprising crude oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substance or their derivatives or a functionally equivalentanalog or derivative and water. Also provided may be a solution to solvethe problem of microbial influenced corrosion (MIC) on solid surfaces,such as surface of the equipment used in the petroleum and natural gasindustries to store, transport, and process raw or refined materials(e.g., crude oil, gas, water, wastewater, production fluids, and otherprocessed substances). Additionally, this disclosure may provide aneffective and cost-effective solution for preventing and/or mitigatingthe formation of harmful biofilms associated with microbialcontamination and/or microbial influenced corrosion of metal surfaces ofthe production, storage, and transport equipment of crude, oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substance.

While the disclosure will be described in conjunction with the exemplaryembodiments, one skilled in the art can understand that it is notintended to limit the disclosure to those embodiments. Any combination,devices or methods provided herein can be combined with one or more ofany of the other combination, devices and methods provided herein. Tothe contrary, this invention is intended to cover alternatives,modifications, and equivalents as may be included within the spirit andscope of the disclosure as defined by the appended claims.

Penetration and Development of Microorganisms

Microorganisms may penetrate into oil fields as a result of drilling,and/or into oil and fuel storage tanks, oil pipelines and transmissionfacilities, which are the perfect place for colonization by both aerobicand anaerobic microorganisms. The stages during which microorganisms mayemerge are commonly: (1) stage of application of drilling fluids, whichmay be contaminated in this way allochthonous bacteria are introduced tothe deposit, (2) stage of supply—borehole watering with highlycontaminated water, (3) stage of oil transport—presence ofmicroorganisms in contaminated water in transmission systems, (4)petroleum processing stage, and (5) stage of storage of crude oil andits processing products. It is extremely difficult to preventmicrobiological contamination because it is impossible to maintainsterile conditions during the extraction, transport and storage of crudeoil. In fact, at each stage of oil processing from its exploitation,transport, processing and ending with the storage, it can be subjectedto the action of microorganisms. Similar routes of contamination existwith water, wastewater, production fluids, soil, air and othersubstances, paper mills and cooling systems.

A necessary condition for the emergence and development ofmicroorganisms is the presence of carbon source in a given environment(e.g., tanks, pipelines, storage, supply systems, etc.). Thedeterioration of crude, oil, gas, hydrocarbons, water, wastewater,production fluids, soil, air and other products under the influence ofmicrobial activity reduces the economic value of the substance becausethey are being used as a carbon source in both aerobic and anaerobicconditions.

Another essential and necessary condition for the growth ofmicroorganisms in crude oil, gas, hydrocarbons, water, wastewater,production fluids, soil, air and other contaminated substance orproducts of its processing is the presence of water, the accumulation ofwater condensation in pipelines during transmission or in the tanksduring storage of the substance. The existence of the possibility ofinteractions between the carbon source and water adds complexity of theissue of microbial contamination, microbial influenced corrosion andbiofilm creation.

Bacteria and fungi are two main groups of microorganisms thatcontaminate the storage, transport and production process of thesubstance. Both bacteria and fungi require food and water to thrive. Ina storage tank their “food” is, for example, oil or other carbon source.They get water from the water that collects in the storage tank and getfood from the carbon-water interface. The resulting microbial slimes(biofilms) are from the unchecked growth of these microorganisms thatare always present in air, fuel, and water. Microorganisms will degradethe production, storage and transport systems if left unmitigated.

MC, MINC, CC, MIC and Biofilms

Microbial contamination (MC), Mineral contamination (MINC), Chemicalcontamination (CC), microbial influenced corrosion (MIC) and/or biofilmformation is frequently observed at the production sites of crude oil,gas, hydrocarbons, water, wastewater, production fluids, soil, air andother contaminated substances and in transport pipelines, and amongother types of equipment involved in the production industry of crudeoil, gas, hydrocarbons, water, wastewater, production fluids, soil, air,and other contaminated substance.

The mechanisms by which microbial contamination (MC), mineralcontamination (MINC), chemical contamination (CC), microbial influencedcorrosion (MIC) and/or biofilm creation causes damage are not fullyunderstood despite many decades of research. However, microbialcontamination (MC), mineral contamination (MINC), chemical contamination(CC), microbial influenced corrosion (MIC) and/or the biofilms createdpose severe operational, environmental, and safety problems to therelated industries, particularly with respect to contamination in crudeoil, gas, hydrocarbons, water, wastewater, production fluids, soil, airand other contaminated substances and corrosion of equipment used in thestorage, processing, and/or transport of the substance. Costs resultingfrom MC, MINC, CC and MIC in these industries due to repair andreplacement of damaged equipment, spoiled products, environmentalclean-up, and injury-related health care, amount to well over severaltens of billions of USDs per year, posing a major economic problem forthe related industries, as well as a huge threat to the environment.

Development and metabolic activity of microflora directly leads to thedeterioration of the physico-chemical parameters of crude oil, gas,hydrocarbons, water, wastewater, production fluids, soil, air, and othercontaminated substance. A negative phenomenon is the precipitation ofbiomass (sludge), which are metabolic products of fungi, bacteria,yeast, etc. The biomass, or sludge, forms larger agglomerates. Thiscauses the silting of reservoir rocks, clogging of pipelines, andaccumulation of sediments at the bottom of storage and transport tanks.The number of microorganisms (bacteria and fungi) in the aqueous layercontained in petroleum products including crude oil, gas, andhydrocarbons, water, wastewater, production fluids, soil, air and othercontaminated substance, determines the amount of contamination.

Also, microbial contamination, mineral contamination, chemicalcontamination and microbial influenced corrosion leads to additionalcorrosion, often characterized by or with pitting of metal surfacescaused by sulfate-reducing bacteria, and frequently results in extensivedamage to the storage, production, and transportation equipment. Pipesystems, tank bottoms, and other pieces of storage and productionequipment can rapidly fail if there are areas where microbial corrosionis occurring. If a failure occurs in a pipeline or storage tank bottom,the released substance can have serious environmental consequences. Morecrucially, if a failure occurs in a high-pressure liquid or gas line,the consequences may be worker injury or death. Any failure at leastinvolves significant repair or replacement costs.

There are several stages during which microbiological, mineral, andchemical contamination of crude oil, gas, hydrocarbons, water,wastewater, production fluids, soil, air and other contaminatedsubstances and their derivatives may occur. In the initial stages ofgrowth, the organisms present are predominantly aerobic, using thedissolved oxygen in the water for respiration. As this supply of oxygenis depleted, anaerobic bacteria (typically known as sulfate-reducingbacteria) develop. These organisms do not require oxygen for respirationand form corrosive waste products. One waste expelled by the organismsis hydrogen sulfide. Sulfate-reducing bacteria also use the enzymehydrogenase, which scavenges hydrogen ions from the metallic surfacesbeneath biofilms. Hydrogenase activity accelerates galvanic corrosion.Other anaerobic bacteria growing produce weak organic acids. The weakorganic acids react readily with chloride, nitrate, nitrite, and sulfateanions to form strong inorganic acids, which attack infrastructuresurfaces.

The microorganisms thought to be primarily responsible for corrosion atleast in an anaerobic environment within the related industries aresulfate-reducing bacteria. Other culpable bacteria includeiron-oxidizing bacteria, sulfur-oxidizing bacteria, nitrate reducingbacteria, methanogens, and acid producing bacteria, among others. Thesecategories of bacteria generally are capable of reducing metal directly,producing metabolic products that are corrosive and/or leading to theformation of biofilms that indirectly alter the local environment topromote corrosion and sludge formation.

Sulfate-reducing bacteria, in particular, are ubiquitous and can grow inalmost any environment. They are routinely found in waters associatedwith production systems of crude, oil, gas, hydrocarbons, water,wastewater, production fluids, soil, air and other contaminatedsubstance and can be found in virtually all industrial aqueousprocesses, including cooling water systems and petroleum refining.Sulfate-reducing bacteria require an anaerobic (oxygen-free) aqueoussolution containing adequate nutrients, an electron donor, and anelectron acceptor. A typical electron acceptor is sulfate, whichproduces hydrogen sulfide upon reduction. Hydrogen sulfide is a highlycorrosive gas and reacts with metal surfaces to form insoluble ironsulfide corrosion products. In addition, hydrogen sulfide partitionsinto the water, oil, and natural gas phases of produced fluids andcreates a number of serious problems. For instance, “sour” oil or gas,which contains high levels of hydrogen sulfide, has a lower commercialvalue than low sulfide oil or gas. Removing biogenic hydrogen sulfidefrom sour oil and gas increases the cost of these products. It is alsoan extremely toxic gas and is immediately lethal to humans at even smallconcentrations. Thus, its presence poses a threat to worker safety.

It is believed that microbial contamination and microbial influencedcorrosion are primarily caused by the formation of microbial biofilms inequipment that comes into contact with crude oil, gas, hydrocarbons,water, wastewater, production fluids, soil, air and other contaminatedsubstance and/or the liquid systems involved in its storage, transportand/or processing.

Biofilms and Treatable Surfaces

Microorganisms present in aqueous environments form biofilms onsurfaces. Biofilm consists of populations of microorganisms and theirhydrated polymeric secretions. Numerous types of organisms may exist inany particular biofilm, ranging from strictly aerobic bacteria at thewater interface to anaerobic bacteria such as sulfate-reducing bacteria(SRB) at the oxygen depleted metal surface.

Biofilm formation is thought to follow a multi-series of specific stepsthat include: (a) an initial bacterial attachment stage that is rapidand reversible; (b) a longer termed attachment stage; (c) a replicationphase; (d) a polysaccharide-rich matrix secretion stage; (e) a biofilmmaturation stage; and (f) finally, a bacterial dispersal stage. Biofilmscan be microns of millimeters to centimeters or more in thickness andcan develop over the course of hours, days, or months, depending on manyfactors that include the consortium of bacteria present and theenvironment.

Biofilms are highly complex, naturally occurring biotic structures whichhave a wide range of characteristics. Their exact role in corrosion isstill under intense study. However, biofilm-associated corrosion is atleast a function of the composition of the underlying bacterialpopulation that forms the biofilm and on the environment. The presenceof biofilm can contribute to corrosion in at least three ways: (1)physical deposition, (2) production of corrosive byproducts, and (3)depolarization of the corrosion cell caused by chemical reaction.

Many of the byproducts of microbial metabolism, including organic acidsand hydrogen sulfide, are corrosive. These materials can concentrate inthe biofilms, causing accelerated metal attack and corrosion. Corrosiontends to be self-limited due to the buildup of corrosion reactionproducts. However, microbes can absorb some of these materials in theirmetabolism, thereby removing them from the anodic and cathodic sites.The removal of reaction products, termed depolarization, stimulatesfurther corrosion.

Biofilms are usually found on solid substrates submerged in or exposedto an aqueous solution, although they can form as floating mats onliquid surfaces and also on the surface of debris, particularly in highhumidity climates. Given sufficient resources for growth, a biofilm willquickly grow to be macroscopic. Biofilms can contain many differenttypes of microorganism, e.g., bacteria, archaea, protozoa, fungi andalgae; each group performs specialized metabolic functions. However,some organisms will form single species films under certain conditions.The social structure (cooperation, competition) within a biofilm highlydepends on the different species present.

Biofilms are held together and protected by a matrix of secretedpolymeric compounds called EPS. EPS is an abbreviation for eitherextracellular polymeric substance or exopolysaccharide, although thelatter one only refers to the polysaccharide moiety of EPS. In fact, theEPS matrix consists not only of polysaccharides but also of proteins(which may be the major component in environmental and wastewaterbiofilms) and nucleic acids. A large proportion of the EPS is more orless strongly hydrated; however, hydrophobic EPS also occur; one exampleis cellulose which is produced by a range of microorganisms. This matrixencases the cells within it and facilitates communication among themthrough biochemical signals as well as gene exchange. The EPS matrix isan important key to the evolutionary success of biofilms and theirresistance to, in this case, biocides and other chemical treatments toremove them. One reason is that it traps extracellular enzymes and keepsthem in close proximity to the cells. Thus, the matrix represents anexternal digestion system and allows for stable synergisticmicroconsortia of different species. Some biofilms have been found tocontain water channels that help distribute nutrients and signalingmolecules.

Despite these protective physical and biological properties of biofilmsand in particular, the EPS which presents a significant permeabilitybarrier to antibacterial agents, oxidizing agents (and oxidizing agentanalogs) has been shown by the inventor to be effective in mitigatingthe formation of biofilms on metal surfaces, in particular, underanaerobic conditions.

Biofilms that form in the substances or on the surfaces of such metalcomponents are thought to be the primary causative agent triggeringcorrosion. Many biofilm-forming environmental bacteria, particularlythose in anaerobic environments, produce harmful gases (e.g., hydrogensulfide), acids (e.g., sulfuric acid), and other agents which are highlycorrosive and also which pose health and safety concerns to thoseworkers in the industry. Currently, mitigation techniques to reducemicrobial induced corrosion are available but are not often effectiveenough and/or are not practical in the industry due to high cost,limited efficacy and other reasons. For example, the use of currentbiocides is common, but their effectiveness is limited due to inabilityto permeate the corrosive biofilms.

EMODs and Synergistic Chemical Reaction

As shown in exemplary embodiments herein, oxidizing agent compositionsand compounds that are functionally equivalent to oxidizing agents, whencombined with radiation of certain wavelengths may significantly reduceunwanted microbial, mineral and chemical concentrations and/or formationof biofilms. Consequently, such compositions and compounds may be usedto reduce, mitigate, or eliminate unwanted microbial, mineral andchemical contaminations in crude oil, gas, hydrocarbons, water,wastewater, production fluids, soil, air and other contaminatedsubstances and/or microbial influenced corrosion on metal surfaces, andin particular, metal surfaces on equipment involved in the storage,transport, and processing of the crude, oil, gas, hydrocarbons, water,wastewater, production fluids, soil, food, air and other contaminatedsubstances.

The interest in environmentally friendly, non-toxic and degradable yetpotent biocides has never been higher. Oxidizing agents have beenextensively used as such biocides, particularly in applications whereits decomposition into non-toxic byproducts is important. The majorityof studies investigating the microbe toxic mechanism of oxidizing agentsconsider them as a source of oxidative stress in the cell to modelchronic oxidative damage to cells. When used to treat microbes,oxidizing agents exhibit non-resistant characteristics, and thus havebroad-spectrum antibacterial and antimicrobial effects. Oxidizingagents, notably hydrogen peroxide (H₂O₂), are increasingly used in anumber of medical, food and industrial applications but also inenvironmental applications. Oxidizing agents and their associated EMODscause many minerals and chemicals to precipitate out of solution. Thiscreates the ability to filter out many of the unwanted minerals andchemicals. This invention increases both the quantity and the functionalduration of EMODs created by the synergistic reaction of an oxidizingagent and certain wavelengths of radiation.

Electronically modified oxygen derivatives (EMODs) are chemicallyreactive chemical species containing oxygen. Examples of EMODs includeperoxides, superoxide, hydroxyl radical, and singlet oxygen. EMODs mayserve as an antimicrobial defense. EMODs may precipitate minerals andchemicals out of solutions. Individuals with chronic granulomatousdisease who have deficiencies in generating EMODs, are highlysusceptible to infection by a broad range of microbes includingSalmonella enterica, Staphylococcus aureus, Serratia marcescens, andAspergillus spp. A role for EMODs in antiviral defense mechanisms alsocan be demonstrated via Rig-like helicase-1 and mitochondrial antiviralsignaling protein. Increased levels of EMODs potentiate signalingthrough this mitochondria-associated antiviral receptor to activateinterferon regulatory factor (IRF)-3, IRF-7, and nuclear factor kappa B(NF-κB), resulting in an antiviral state.

EMODs may be generated through a synergistic chemical reaction ofoxidizing agents and ionizing/nonionizing radiation. In a chemicalcompound, these generated EMODs are in addition to the commonlyoccurring EMODs that are utilized currently in industry and science.During the process that the radiation and the oxidizing agents interact,damaging intermediates may be created. Oxidizing chemicals may be usedas the precursors to EMODs, while the radiation may function as anexogenous source. This type of synergistic reaction may lead to asituation where the resulted antimicrobial effect is much greater thanthe sum of the effect caused by individual components of the reaction.In addition, EMODs created by this synergistic reaction exist muchlonger than the expected life of nanoseconds that current literaturedescribes. EMODs generated by this synergistic reaction exist forlengths of time previously undiscovered. This previously undiscoveredlength of time can be seconds, minutes, hours and days. For example,EMODs can last 1 minute, 5 minutes, 10 minutes, 30 minutes, 1 hour, 12hours, 24 hours, 2 days, 5 days or 7 days. The EMODs presence isdemonstrated by a continued antimicrobial effect, or reduction inmicrobial content during a given time period, as compared to a control.Due to the higher concentration of EMODs, this new discovery allows forgreater functionality of a specific concentration of an oxidizing agentthen is currently available from that concentration. For example, 0.3%of hydrogen peroxide that is exposed to radiation as described, mayproduce similar antimicrobial effects as 3% hydrogen over a 12 hourperiod. Additionally, this discovery allows for the synergistic reactionbetween an oxidizing agent and certain wavelengths of radiation to takeplace minutes, hours, or days before this compound that exhibitsincreased functionality is applied to a target. By utilizing the higherconcentration of EMODs, this results in economic savings and a moreenvironmentally friendly method of eliminating unwanted MC, MIC, MINC,and CC.

In the synergistic reaction process, water loses an electron and becomeshighly reactive. Then through a three-step chain reaction, water issequentially converted to hydroxyl radical (.OH), hydrogen peroxide(H₂O₂), superoxide radical (.O⁻²) and ultimately oxygen (O₂). Thehydroxyl radical is extremely reactive and immediately removes electronsfrom any molecule in its path, turning that molecule into a free radicaland thus propagating a chain reaction. Actually, hydrogen peroxide iseven more damaging to DNA of microbes than the hydroxyl radical, becausethe lower reactivity of hydrogen peroxide provides enough time for themolecule to travel into the nucleus of the cell, subsequently reactingwith macromolecules such as DNA.

This discovery may find application in reducing microbial, mineral andchemical concentrations. As an example, a 3% solution of hydrogenperoxide can be expected to eliminate approximately 30% of microbes thatare exposed to it. Radiation of a wavelength between 300 nanometers and600 nanometers can be expected to eliminate 3% of the microbes exposedto it. However, when 3% hydrogen peroxide and radiation of a wavelengthbetween 300 nanometers and 600 nanometers are administered together, theresulted synergistic reaction may eliminate 99.9999% of microbes exposedto the compound for minutes, hours and days. This is an example of thesynergistic reaction and the residual effect of the generated EMODs.

Also, this discovery may find application in elimination and reductionof bacterial biofilms. In an example, a biofilm of bacteria was exposedto light of wavelengths of 300 to 600 nm for 30 to 60 seconds while inthe presence of 3 to 300 mM of an oxidizing agent. Microbial counts fromeach treated sample were compared with those of the control samples. Theresults showed that the combination of the light and oxidizing agentsuccessfully penetrated all layers of the biofilm, creating an excellentantibacterial effect. The ability of noncoherent light in combinationwith the oxidizing agent to affect bacteria in deep layers of biofilmillustrates that this treatment may be applied in biofilm-relatedmicrobial contamination, microbial influenced corrosion and biofilmelimination as a minimally invasive antibacterial procedure.

Combination of Oxidizing Agent Compositions and Radiation

New research demonstrates that compositions containing oxidizing agentsmay undergo the synergistic reaction with certain wavelengths ofradiation, before the compound is applied to a target, after thecompound is applied to the target or while the compound is applied tothe target. This presents a tremendous advantage over current methods.Oxidizing agent compounds administered together with radiation ofcertain lengths to crude oil, gas, hydrocarbons, water, wastewater,production fluids, soil, air and other contaminated substances, or tosurfaces in need of treatment for the effective mitigation and/orelimination of microbes, minerals, chemicals and biofilms, andparticularly, microbes and biofilms in anaerobic conditions. Exemplaryembodiments shown and described herein show that oxidizing agents andcompounds that are functionally equivalent to oxidizing agents can forma synergistic reaction when combined with radiation of certainwavelengths. In particular embodiments, such combination of oxidizingagent compositions and radiation may significantly reduce microbial,mineral and chemical concentrations in the targeted hydrocarbon and/orreduces the formation of biofilms on liquid surfaces and on equipment,and consequently may be used to reduce, mitigate, or eliminate microbialcontamination, mineral contamination, chemical contamination and/ormicrobial influenced corrosion on metal surfaces, in particular, metalsurfaces on equipment involved in the storage, transport, and processingof the crude oil, gas, hydrocarbons, water, wastewater, productionfluids, soil, air and other contaminated substances. Such equipment maybe pipelines, storage tanks, cooling system (closed or open loopsystem), transport equipment, and refinement processing equipment.

In some embodiments, the oxidizing composition in combination withradiation may be extremely effective in reducing, eliminating, orblocking biofilm formation in anaerobic environments, which was notpreviously known or appreciated.

Oxidizing agents may be those synthesized by a variety of methods.Oxidizing agents and their derivatives may be obtained commercially froma wide range of sources that will be known by the skilled artisan.Oxidizing agents may also be naturally occurring. Oxidizing agents arewidely distributed in the natural environment and can be produced by avariety of bacteria. For example, oxidizing agents can be produced bybacteria as a degradation product. As an intercellular signal molecule,H₂O₂ regulates various aspects of bacterial physiology. Table 1 listscommon oxidizing agents and their corresponding products as non-limitingexamples.

TABLE 1 Oxidizing Agents Product(s) oxygen (O₂) Various products,including the oxides H₂O and CO₂ peracetic acid Various products,including H₂O, O₂, and CO₂ ozone (O₃) Various products, includingketones, aldehydes, and H₂O; see ozonolysis fluorine (F₂) F⁻ chlorine(Cl₂) Cl⁻ bromine (Br₂) Br⁻ iodine (I₂) I⁻, I⁻ ₃ hypochlorite (ClO⁻)Cl⁻, H₂O chlorate (ClO⁻ ₃) Cl⁻, H₂O nitric acid (HNO₃) nitric oxide(NO)NO₂ nitrogen dioxide SO₂ (sulfur dioxide) sulphur (ultramarineproduction, commonly reducing agent) Hexavalent chromium Cr³⁺, H₂O H₂O₂,other peroxides Various products, including oxides and H₂O

The disclosed invention also contemplates the use of oxidizing agentanalogs or equivalent compounds. “Oxidizing agent equivalent” or“oxidizing analog or functionally equivalent compound, molecule orderivative” or similar terms may include any known or yet unknowncompounds that have a structure that is similar to oxidizing agents to adegree such that they can produce the same or similar biological effectsas oxidizing agents. Such analogs or functionally equivalent compoundsmay be obtained in various ways, including isolation from nature,chemical modification, or via chemical synthesis.

In certain embodiments, the oxidizing agent compositions combined withradiation for use in the exemplary methods may be prepared to have anyuseful properties that may be appropriate or advantageous to theparticular substance or surface to be treated. The exact ingredient ofthe oxidizing agent compositions may depend on various factors, e.g.,whether the substance/surface to be treated is under aerobic oranaerobic conditions, the pH and salinity of the substance/surface to betreated, the consortium or population characteristics of the bacteriapresent in the biofilm of the target substance/surface to be treated,the type and composition of minerals and chemicals that may be targeted,the properties of the biofilm to be treated, among othercharacteristics.

The oxidizing agent compositions combined with radiation may alsoinclude components that may help stabilize and/or improve the oxidizingagents as the active ingredient, or components that may facilitatedelivery of the oxidizing agents. For example, the oxidizing agentcompositions herein described may also include surfactants or disruptionagents and the like which may increase the permeability and/ordisruption of the biofilm to facilitate the movement of the oxidizingagent composition into the biofilm and into contact with the bacteriatherein.

Surfactants are well known in the art and include anionic surfactants(e.g., ammonium lauryl sulfate, sodium lauryl sulfate (SDS, sodiumdodecyl sulfate, another name for the compound), sodium lauryl ethersulfate (SLES), and sodium myreth sulfate; sodium stearate, sodiumlauroylsarcosinate), cationic surfactants (Octenidine dihydrochloride,Cetylpyridinium chloride (CPC), Benzalkonium chloride (BAC),Benzethonium chloride (BZT), 5-Bromo-5-nitro-1,3-dioxane,Dimethyldioctadecylammonium chloride, Cetrimonium bromide, Dioctadecyldimethylammonium bromide (DODAB)), and nonionic surfactants(Polyoxyethylene glycol alkyl ethers, Polyoxypropylene glycol alkylethers, Glucoside alkyl ethers, Polyoxyethylene glycol octylphenolethers (e.g., Triton-X), Polyoxyethylene glycol alkylphenol ethers,Glycerol alkyl esters, Polyoxyethylene glycol sorbitan alkyl esters,Polyethoxylated tallow amine (POEA)), as well as biosurfactants (surfaceactive substances synthesized by living cells).

When administering the oxidizing agent composition in combination withradiation of certain wavelengths to a site targeted for treatment (e.g.,a surface having MIC, MINC, CC or a substance having MC), thecomposition may be administered or delivered in an amount or dosagesufficient to provide an effective amount of the oxidizing agentcomposition in combination with radiation or oxidizing agent compositionanalog in combination with radiation. The term “effective amount of theoxidizing agent or oxidizing agent analog” is the minimal amount, level,or concentration of the oxidizing agent or oxidizing agent analog whichresults in a measurable or detectable effect on the substance or metalsurface to be treated, in particular, on the MC, MINC, CC, MIC or theassociated biofilm itself. Due to the increased EMODs generated by themethod of this invention, the effective amount of the oxidizing agentwill be lower than previous applicable concentrations. The effectiveamount can be measured in terms of concentration as parts-per-million(ppm), percentages or any suitable measurement.

In certain embodiments, the effective amount of theoxidizing-agent-containing compositions provides a concentration of theoxidizing agent compound that is between about 0.001 percent to 100percent or more of the volume of the hydrocarbon or other substance tobe treated, such as between about 0.001 percent and about 1 percent, orbetween about 0.001 and about 50 percent. However, it will be clear to aperson skilled in the art that this term may refer to any suitableconcentration that is necessary to achieve the desired effects.

Although any treatment methods similar or equivalent to those describedherein can also be used in the practice or testing of the presentdisclosure, some exemplary methods are now described.

Treatment Methods and Applications

As shown in the exemplary embodiments, the combination of oxidizingagents and radiation of certain wavelengths may form a synergisticreaction. The synergistic reaction may generate EMODs, which may beeffective in reducing microbial count, mineral contamination, chemicalcontamination and eliminating or blocking biofilm formation,particularly in anaerobic environments. Prior to the invention describedin this disclosure, this synergistic reaction involving oxidizing agentsand radiation of certain wavelengths was not known or appreciated as toits relationship to EMOD creation and EMOD longevity or its effect onmicrobial contamination (MC), mineral contamination (MINC), chemicalconcentration (CC), microbial influenced corrosion (MIC) or biofilmcreation. MC, MINC, CC, MIC and biofilm may be eliminated or greatlyreduced with the disclosed treatment methods in or on equipmentincluding pipelines, storage tanks, transport and refinery processingequipment.

In one aspect, the embodiment may relate to a method for reducingmicrobial concentration, mineral contamination, chemical contaminationor for reducing biofilm formation to mitigate or eliminate microbialcontamination, mineral contamination, chemical contamination and/ormicrobial influenced corrosion on a metal surface. The method mayinclude contacting the substance or metal surface to be treated with aneffective amount of a composition comprising an oxidizing agent or afunctionally equivalent analog or derivative thereof, and exposing theresulted mixture of the substance or metal surface to be treated and thecomposition to radiation of certain wavelengths. The radiation may beapplied to the oxidizing agent before it is applied to the target, whileit is applied to the target or after it is applied to the target. Thisaspect of the invention has not been previously reported in literature.The ability to greatly increase the performance of an oxidizing agentbefore it is applied to a target creates new application modalities. Theoxidizing agent and the radiation together form a synergistic reaction,resulting in an antimicrobial effect that is stronger than the sum ofthat of the oxidizing-agent-based composition and radiation when actingseparately. The synergistic reaction also creates EMODs that exist forseconds, minutes, hours and days. The discovery of the existence ofEMODs that last for longer than a few nanoseconds is a new andpreviously unreported, undiscovered, property of the technologydescribed in this patent application. In other aspects, the disclosuremay relate to corresponding combination and device for reducingmicrobial concentration, mineral contamination, and chemicalconcentration or for reducing biofilm formation to mitigate or eliminatemicrobial contamination, mineral concentration, chemical concentrationsand/or microbial influenced corrosion on a metal surface.

The method disclosed herein may also include additional upstream and/ordownstream testing steps that facilitate knowing whether and how toadminister the treatment involving an oxidizing agent compositioncombined with radiation of certain wavelengths. Such additional stepsmay aim to determine whether a target system has a legitimate MC, MINC,CC and/or MIC risk at a particular site (e.g., a crude pipeline thattransports crude oil from an offshore rig to a distant domesticrefinery). Other steps may also involve subsequent monitoring steps toevaluate the extent of the MC, MINC, CC and MIC associated biofilm,followed then by steps to carry out a particular treatment plan of theoxidizing agent composition compound combined with radiation of certainwavelengths, e.g., an aggressive treatment plan or a lower strengthtreatment plan.

For example, corrosive damage to a pipeline may be detected as a resultof regularly scheduled maintenance along a certain ten-mile stretch ofcrude oil pipeline. In order to learn more about the extent and natureof the damage, and therefore to determine an appropriate treatment, auser may sample the environmental conditions at various points along thepipeline by assessing properties that would be indicative of conditionssuitable for biofilm formation, including, but not limited to: (a)detection of certain bacterial species known to have a role in bacterialcorrosion (e.g., sulfate reducing bacteria), (b) detection of certaincorrosive metabolites (e.g., presence of organic acids, hydrogen sulfidegas, or the like), (c) existence of suitable pH and temperatureconditions known to be supportive of biofilm development, (d) presenceof an aqueous environment (e.g., extent of water dropout or separationof a water phase from the crude oil), (e) slow flow rate (which is knownto be conducive to biofilm formation), and (f) existence of highbacterial biomass. The person of ordinary skill may also wish to examinephysical samples collected from the pipeline wall to detect andcharacterize the biofilm (e.g., thickness) or metal coupon samplesplaced into the flow path. Such factors may be evaluated and thenassessed by the skilled person to design a specifically tailoredoxidizing agent compound combined with radiation of certain wavelengths,resulting in a synergistic-reaction-based treatment. This synergisticreaction creates EMODs that exist for longer periods of time then haspreviously ever been recorded. This characteristic of this disclosureallows treatments of these issues with lower levels of oxidizing agentsand it allows for a treatment that lasts for a greater period of timewhen compared to a similar dose of an oxidizing agent from methods thatwere in use previously to this disclosure.

In some embodiments, variables affecting the specific nature of anygiven synergistic-reaction-based treatment involving oxidizing agentcompounds combined with radiation of certain wavelengths may include,for example: (a) pH of the oxidizing agent compound composition, (b)salinity of the oxidizing agent compound composition, (c) concentrationof the oxidizing agent compound in the composition (e.g., 1%, 2%, 5%,10%, 50%, w/v), (d) target or desired concentration of the oxidizingagent compound composition once delivered in the flow path (e.g., 1 ppm,2 ppm, 4 ppm, 10 ppm, 50 ppm, 100 ppm, 500 ppm, 1000 ppm or more), (e)the rate of flow of the substance to be treated, (f) the rate ofinjection of the oxidizing agent compound composition, (g) the types ofbacteria present in the consortium of the biofilm, (h) the level ofbacterial biomass and/or biofilm present, (i) the presence of visibleevidence of corrosion (e.g., pits) (which generally is associated withthe degree of corrosion in an increasing linear relationship), and (j)the detection of metal loss on test coupons. Each of these factors maybe assessed, along with other available factors, to gauge the severityof the MC, MINC, CC and MIC risk and/or the degree of biofilm-associatedcorrosion. Once the severity of the corrosion is known, the skilledperson can determine the best course for administering the treatment(i.e., the oxidizing agent compound composition combined with radiationof certain wavelengths).

Treatment may be aggressive in nature, or otherwise less aggressive,depending on the degree and severity of the MC, MINC, CC and/or MICand/or biofilm formation. For example, if the degree of biofilmassociated corrosion is determined to be low, a gentle treatment may beadministered by, for example, reducing the total amount or concentrationof the oxidizing agent compound composition combined with radiation ofcertain wavelengths delivered, reducing the number of hours of continuedinjection into the site of interest, or increasing the number of daysspanning between follow-up injections. However, if the degree of biofilmassociated corrosion is determined to be high, a more aggressivetreatment may be administered by, for example, increasing the totalamount or concentration of the oxidizing agent compound combined withradiation of certain wavelengths delivered, increasing the time periodfor continuous injection, or shortening the number of time or daysbetween successive treatments.

The oxidizing-agent-based compositions combined with radiation ofcertain wavelengths of the disclosure may be used to treat any affectedsurface, and in particular, any affected metal surface on any equipmentinvolved in the storage, transport, and/or processing of the substanceto be treated. For example, affected surfaces may include a pipelinethat transports crude oil from onshore or offshore drill site or fromhydraulic fracturing sites to local or distant petroleum and/or naturalgas refineries. Problematic biofilms may form along the interiorsurfaces of wastewater pipelines over distances that extend over manymiles or tens of miles, leading to corrosive conditions over a multitudeof points. It is generally accepted that pipeline corrosion representsthe majority of corrosive damage due to MC, MINC, CC and MIC intransport of the substance, particularly given that there are over190,000 miles of liquid pipelines in the US alone. In another example,affected surfaces may include storage facilities at refinery sites orthose located on transport tankers. Other equipment, such as pumps,valves, and other equipment that comes into contact with the flow pathof the substance, is susceptible to the formation of biofilms and thusto MC, MINC, CC and MIC. Any and all of these sites and surfaces may betreated using the methods disclosed herein.

Exemplary FIG. 1 depicts a diagram showing an embodiment in which themethod is applied in a storage tank of crude oil, gas, hydrocarbons,water, wastewater, production fluids, soil, air or other contaminatedsubstance. As illustrated in FIG. 1, water 10 is accumulated on thebottom of the tank during storage of the substance 20. The substance 20has a density or specific gravity less than that of water, and thusfloats on the surface of water 10. Typically, bacteria and/or fungi thatinvade the tank thrive at the interface between the substance layer andthe water layer, obtaining water from water 10 while obtaining carbon as“food” from the substance 20. Also, the greatest microbial contamination(MC) normally occurs at the substance-water interface because thebacterial life is well supported there. Moreover, at the locations 50where the substance-water interface touches the metal tank, the greatestmicrobial influenced corrosion (MIC) may be observed. The rapid growthof the microorganisms such as fungi, bacteria, yeast at thesubstance-water interface not only leads to formation of corrosivebiofilms, their metabolic products may further form larger agglomerates,causing precipitation of sludge 30 on the bottom of the tank. Microbialinfluenced corrosion (MIC) may be observed at the locations where sludge30 touches the metal tank as well.

In the method according to this exemplary embodiment, an effectiveamount of the composition comprising the oxidizing agent compound, or afunctionally equivalent analog or derivative thereof may be administeredinto the substance to be treated. In certain embodiments, the effectiveamount of composition may be administered into the water that exists inthe tank. Because the microbes require water to survive and multiply,treating the water with the oxidizing agent while exposing the mixtureto certain wavelengths of radiation creates EMODs that reduce oreliminate the MC, MINC, CC MIC and/or biofilm. In some embodiments, thecomposition comprising the oxidizing agent compound may be introducedinto the tank via a pump or other automated means. In other embodiments,the oxidizing-agent-based composition may be introduced manually.

A radiation emission mat 41 may be arranged inside the storage tank,near to the target areas to be treated. A typical target area may be theinterface between water and the substance to be treated. With itsdensity or specific gravity properly calibrated, the radiation emissionmat 41 can be kept in the storage tank at a desired location, e.g.,floating at the substance-water interface, suspended from an anchorelement above the storage tank or above the desired location of disposalof mat 41, supported and held in place by an anchor element at or near abottom portion of a storage tank, or otherwise fixed in place in thestorage tank through any fixing elements, as desired. The radiationemission mat 41 may emit radiation of certain wavelengths, e.g., awavelength between 300 nm and 600 nm. In certain embodiments, theradiation emission mat 41 is movable so that it may be controlled tostay at a desired location relative to the target areas. The wavelength,intensity and/or time of duration of the radiation emitted from the mat41 also may be adjustable, for example a wavelength between 300 nm and600 nm.

FIG. 2 depicts a diagram showing another exemplary embodiment in whichthe method is applied in a storage tank of crude oil, gas, hydrocarbons,water, wastewater, production fluids, soil, air or other contaminatedsubstance. As illustrated in FIG. 2, the substance 20 has a density orspecific gravity greater than that of water, and thus water 10 that isaccumulated in the storage tank is floating on the surface of thesubstance 20. Similarly, the greatest microbial contamination (MC) maybe observed at the substance-water interface, and the greatest microbialinfluenced corrosion (MIC) at the locations 50 where the substance-waterinterface touches the metal tank. Microbial influenced corrosion (MIC)may be observed at the locations where sludge 30 touches the metal tankas well.

Oxidizing agent compounds may be similarly introduced into the storagetank manually, by a titration system, or via a pump. At least oneradiation emission mat may be arranged inside the tank, near to thetarget areas to be treated. The target areas may include, but are notlimited to, the substance-water interface and the bottom of the storagetank. In certain embodiments, with their density or specific gravityproperly designed, a radiation emission mat 41 may be arranged floatingat the substance-water interface, while a second radiation emitting mat42 may be provided as resting on the bottom of the storage tank, near tosludge 30. The radiation emission mats 41 and 42 may emit radiation ofcertain wavelengths, for example a wavelength between 300 nm and 600 nm.

Exemplary FIG. 3 depicts a diagram showing an embodiment in which themethod is applied in a length of transport pipeline. The presentembodiment may be used in a length of pipeline of crude oil, gas,hydrocarbons, water, wastewater, production fluids, air or othercontaminated substances. In this embodiment, a band 70 with radiationproducing function may be arranged inside the pipeline 60, in the formof a lining layer on the wall of the pipeline 60. An effective amount ofa composition comprising an oxidizing agent compound, or a functionallyequivalent analog or derivative thereof may be administered into thepipeline 60. The radiation producing band 70 may emit radiation ofcertain wavelengths, for example a wavelength between 300 nm and 600 nm.

Referring now to exemplary FIG. 4, in this embodiment treatment can beprovided in various stages. Here, the substance to be treated 80 flows,is pumped, or is otherwise put into tank 81, which could also be a pipe,pipeline, storage container, or the like. Tank 81 is such that substanceto be treated 80 is mixed or interspersed with an oxidizing agent 87, asdescribed throughout the exemplary embodiments. The oxidized substanceto be treated 80 then flows through conduit 82 into tank 83. In tank 83,the oxidized substance to be treated 80 is exposed to radiation 86 tocause the synergistic reaction. Treated substance 85 then flow outthrough conduit 84 to a desired location. For example, treated substance85 could flow to another storage tank that is commutatively coupled totank 81. Alternatively, treated substance 85 could be transported via afurther pipe or pipeline to another location.

The method can further be implemented in the form of a closed loop oropen loop system so as to decontaminate the substance in a storage tank,transport device, pipeline or other area where contamination may occur.Exemplary FIG. 5 depicts a diagram showing an embodiment in which themethod is applied in the form of a closed loop system fordecontaminating a substance to be treated, whereas exemplary FIG. 6depicts a diagram showing exemplary an embodiment in which the method isapplied in the form of an open loop system for decontaminating asubstance to be treated. An oxidizing agent is added to the contaminatedsubstance and the oxidizing agent is exposed to certain wavelengths ofradiation before it's added to the contaminated substance or while it'sadded to the contaminated substance or after it is added to thecontaminated substance. Exemplary FIG. 7 depicts a diagram showing anembodiment in which the method is applied in the form of an oxidizingagent compound that is exposed to radiation of a certain wavelength in areservoir before the oxidizing agent compound is administered to thetarget substance to be treated This oxidizing agent compound may beirradiated to initiate the synergistic reaction before the oxidizingagent compound is applied to the target, while the oxidizing agent isapplied to the target, after the oxidizing agent is applied to thetarget or a combination of these methods. The synergistic reactioncreates EMODs that destroy microbes and precipitates contaminates. TheseEMODs exist for a previously undiscovered time consisting of seconds,minutes, hours and days. This is in contrast to the previously recordedtime life of EMODs that was a few nanoseconds.

The system depicted in FIG. 5 is, for example, suitable fordecontamination of a substance in a reaction container 33. The system isprovided with a float 22, which has a specifically designed structureand specific gravity that allows it to rest in a layer where microbesand/or contaminants are concentrated, e.g., the interface of oil andwater. A circulating pump 11 equipped with sensors injects a desiredamount of oxidizing agent compound into the reaction container 33. Thisinjected oxidizing agent compound may have been exposed to radiationcreating the EMOD generating synergistic reaction before it was appliedto the target, while it was applied to the target, after it was appliedto the target or a combination of the three. After the synergisticreaction takes place, the oil is returned to its storage container, forexample, oil tanks. Although FIG. 5 shows an instance in which thesystem is applied for decontamination of oil, it will be understood thatthis system can be used to decontaminate various other contaminatedsubstances as needed.

The system depicted in FIG. 6 is, for example, suitable fordecontamination of a substance flowing in a pipeline 33. In thisexemplary embodiment, an oxidizing agent injector 11 equipped withsensors is arranged in the upstream of a radiation emitting device 22.This injected oxidizing agent compound may have been exposed toradiation creating the EMOD generating synergistic reaction before itwas applied to the target, while it was applied to the target, after itwas applied to the target or a combination of the three. After thesynergistic reaction takes place, the treated substance continuesflowing further downstream for its intended use or further storage.

In certain embodiments, various sensors may be provided to detectvariables including, but not limited to pH, temperature, density, oxygenconcentration of the substance stored in the tank or transported throughthe pipeline. Further, the effective amount of the compositioncomprising the oxidizing agent compound, or a functionally equivalentanalog or derivative thereof may be determined on the basis of any oneor more of the density and light absorbing quality of the substance tobe treated, and the size and shape of the container (tank, pipeline, orthe like) thereof.

In certain embodiments, the formulation of the oxidizing agentcomposition may be determined on the basis of whether the substance tobe treated is under aerobic or anaerobic conditions, pH of thesubstance, salinity of the substance, consortium or populationcharacteristics of the microorganism present in the substance, themicrobial content of the substance and/or the microbial content of thebiofilms.

In certain embodiments, the wavelength, intensity, duration time and/orlocation relative to the substance to be treated, of the radiation, maybe determined on the basis of any one or more of the density and lightabsorbing quality of the substance, the size and shape of the containerthereof, whether the substance is under aerobic or anaerobic conditions,pH of the substance, salinity of the substance, consortium or populationcharacteristics of the microorganism present in the substance, and themicrobial content of the biofilms.

In certain embodiments, the person of ordinary skill in the art willeasily be able to assess the degree of biofilm associated corrosion orcontamination based on various measurable inputs and accordinglydetermine a proper course of the oxidizing agent compound combined witha radiation of certain wavelengths without undue experimentation.

Combination Treatments

Exemplary embodiments shown and described herein relate, in part, to thediscovery that oxidizing agents or compounds that are functionallyequivalent may form a synergistic reaction together with radiation ofcertain wavelengths. The resulting synergistic reaction may result in aproduct that may significantly reduce the formation of microbes, mineralcontamination, chemical contamination and biofilms in the substance tobe treated and on surfaces, and consequently, may be used to reduce,mitigate, or eliminate microbial contamination, mineral contamination,and/or chemical contamination associated with the substance to betreated and/or microbial influenced corrosion on metal surfaces, inparticular, metal surfaces on equipment involved in the storage,transport, and processing of the substance to be treated. In particularembodiments, the product of the synergistic reaction involving theoxidizing agents and radiation, EMODs, may be effective in reducing,eliminating, or blocking microbes and biofilm formation in anaerobicenvironments, which prior to the disclosure was not known orappreciated. Such equipment can include pipeline, storage tanks, supplysystems and processing equipment.

The synergistic reaction associated with oxidizing agents and radiationmethodologies herein disclosed may be advantageous over existingmitigation practices at least because: (a) the oxidizing agents may be anatural product of environmental bacteria, hence minimal environmentalimpact compared to currently available biocides; (b) current biocidesare naturally taken up by bacteria in a biofilm and induce a switch toplanktonic growth behavior (i.e., growth away from biofilm environment)and thus, lack biofilm permeability aspects needed to better eliminateMC, MINC, CC and MIC; (c) this MC, MINC, CC and MIC eliminating orreducing treatment may be compatible with commercial corrosioninhibitors, whereas many current biocides are not; (d) Further, thesynergistic reaction between the oxidizing agents and the radiationpresents no negative environmental impact, which is unique compared withcurrent methods of treating MC, MINC, CC and MIC, and thus thisinvention results in a more complete elimination or reduction in MC,MINC, CC and MIC than currently available methods; and (e) the reductionin MC, MINC, CC and MIC is significantly greater than currentlyavailable methods.

Moreover, the disclosed synergistic reaction treatment methods involvingoxidizing agent compound combined with radiation of certain wavelengthsmay be also contemplated to be combined with other MC, MINC, CC and/orMIC mitigation strategies, such as the use of corrosion resistantmetals, temperature control, pH control, radiation, filtration,protective coatings with corrosion inhibitors or other chemical controls(e.g., biocides, oxidizers, acids, alkalis), bacteriological controls(e.g., phages, enzymes, parasitic bacteria, antibodies, competitivemicroflora), pigging (i.e., mechanical delamination of corrosionproducts), sonication, stirring (the introduction of movement in thesubstance to be treated), anodic and cathodic protection, and modulationof nutrient levels.

For instance, in certain embodiments relating to pipeline treatment, thepipeline may be first treated with pigging. The pigging can help notonly to physically remove the biofilm, but also acts to disturb thebiofilm such that the permeation of the biofilm is improved, therebyrendering the synergistic reaction treatment involving oxidizing agentcompounds combined with radiation of certain wavelengths more effective.Methods and equipment for pigging pipelines are well known in the artand thus are not described in detail here.

EXAMPLES

This disclosure may be further demonstrated by the following exampleswhich should not be construed as limiting. The contents of allreferences, including any publicly available polypeptide and/or nucleicacid sequences accession numbers (e.g., GenBank), and published patentsand patent applications cited throughout the application are herebyincorporated by reference. Persons of ordinary skill in the art willrecognize that the disclosure may be practiced with variations on thedisclosed structures, materials, compositions and methods, and suchvariations are regarded as within the ambit of the disclosure.

Example 1

Example 1 may demonstrate reduction of MC, MINC, CC and MIC associatedwith Desulfoviberio vulgaris Hildenborough (DvH) growing on carbon steelin the presence of oxidizing agent compounds combined with radiation ofcertain wavelengths which may result in a synergistic reaction.

In Example 1, carbon steel coupons were incubated in the presence ofoxygen and, as the oxidizing agent compound, hydrogen peroxide, combinedwith radiation of certain wavelengths of 300 nm to 500 nm in asynergistic reaction, with and without an inoculum of DvH. The metalloss of the carbon steel coupons was measured. The results show thatcoupons incubated with DvH experienced approximately a 2-fold moreweight loss than those incubated in a sterile environment. Additionally,the data shows that oxidizing agent compounds combined with radiation ofcertain wavelengths of 300 nm to 500 nm in a synergistic reactioncreates EMODs that reduce and/or eliminate corrosion in the presence ofDvH (MIC) compared to the no oxidizing agent compound combined withradiation of certain wavelengths of 300 nm to 500 nm in a synergisticreaction treatment, and that this reduction in weight loss is notreplicated in a sterile environment without DvH inoculation. Therefore,the experiment demonstrates that oxidizing agent compounds combined withradiation of certain wavelengths in a synergistic reaction hasinhibitory effect on corrosion is MIC specific.

Example 2

Example 2 may demonstrate that microbial contamination MC, mineralcontamination (MINC), chemical contamination (CC) and Microbial InducedCorrosion (MIC) by DvH is reduced by different concentrations 100 ppm,or 0.01%, of the oxidizing agent compound hydrogen peroxide combinedwith radiation of certain wavelengths at 300-500 nm in a synergisticreaction.

In example 2, steel coupons were incubated in cultures of DvH for threedays with and without exposure to an oxidizing agent compound,specifically hydrogen peroxide, combined with radiation of certainwavelengths 300-500 nm in a synergistic reaction and then the couponswere measured to determine the amount of metal loss due to corrosion.Coupons incubated in the absence of an oxidizing agent compound combinedwith radiation of certain wavelengths in a synergistic reaction resultedin nearly 2-fold more metal loss than the coupons grown in the presenceof an oxidizing agent compound combined with radiation of certainwavelengths in a synergistic reaction. The data demonstrates that themetal coupons in the presence of the oxidizing agent compound combinedwith radiation of certain wavelengths in a synergistic reactiondisplayed little to no corrosion. Therefore, the experiment demonstratesthat oxidizing agent compounds combined with radiation of certainwavelengths in a synergistic reaction inhibit corrosion of metal causedby anaerobic biofilms formed from sulfate-reducing bacteria.

Example 3

Example 3 may demonstrate the treatment of a pipeline with an oxidizingagent compound, hydrogen peroxide, combined with radiation of certainwavelengths 300-500 nm in a synergistic reaction to inhibit microbialinfluenced corrosion, mineral contamination, chemical contamination andassociated biofilm formation

In example 3, steel pipelines are used to transport seawater fromtreatment and pumping facilities to oil field water injection wells. Thewater is injected into specific regions of an oil-producing reservoir toprovide secondary oil recovery. This provides additional oil recoveryover that which results from primary, or natural, production due to theinitial pressurization of the reservoir.

Treatment of the seawater prior to entering the pipeline is required toprevent corrosion of the steel pipeline and the steel tubing in thewater injection wells and to improve injected water quality. Thetreatment process may include chlorination, filtration, deaeration, andaddition of a solution of an oxidizing agent compound combined withradiation of certain wavelengths in a synergistic reaction. Thechlorination kills the majority of the bacteria and algae entering thesystem with the water from the sea. The filtration removes most of thesea sediments, large particles, and biomass. Deaeration of the water iscritical to remove oxygen, a key element involved in the corrosionprocess. Deaeration of the seawater to less than about 20 ppb oxygenessentially eliminates the potential for common oxygen-inducedcorrosion. Unfortunately, removing the oxygen results in an anaerobicenvironment, which increases the potential for anaerobic corrosion ofthe steel pipeline due to the activity of sulfate-reducing bacteria inthe system and other categories of bacteria. Addition of a solution ofan oxidizing agent (or functionally equivalent analog thereof), such ashydrogen peroxide, combined with radiation of certain wavelengths, suchas 300-500 nm, in a synergistic reaction will be introduced to controlthe activity of the corrosion inducing sulfate-reducing bacteria andother biofilm-forming bacteria that lead to corrosion, such asiron-oxidizing bacteria, sulfur-oxidizing bacteria, nitrate reducingbacteria, methanogens, and acid producing bacteria, among others. Also,the addition of a solution of an oxidizing agent (or functionallyequivalent analog thereof) combined with radiation of certainwavelengths in a synergistic reaction will be introduced to removedunwanted concentrations of mineral and chemicals.

Example 4

Example 4 may demonstrate that MC by anaerobic bacteria Staphylococcusepidermidis ATCC 12228 with or without the presences of MNC, by iron, isreduced by either 3% or 0.3% hydrogen peroxide as the oxidizing agentcompound combined with radiation of certain wavelengths at 400 nm to 420nm, thereby providing a synergistic reaction. Moreover, the resultsdemonstrate that the oxidizing agent compound can be exposed toradiation prior to contact with the target and exposed to radiation asecond time to reactivate of the antimicrobial effect.

Specifically, solutions of 3% hydrogen peroxide, 0.3% hydrogen peroxide,3% hydrogen peroxide with iron (20 mL of 3% H₂O₂ with 0.5 mL of 0.1NFeSO₄) and 0.3% hydrogen peroxide with iron (2 mL of 3% H₂O₂ with 18 mLof Sterile DI Water and 0.5 mL of 0.1N FeSO₄) were tested. Each testsubstance was treated with light of 400 to 420 nm for 1 minute, thenapplied to a target (a carrier with a viable bacteria concentration ofapproximately 1×10⁶ cells or greater). The solutions were applied to thetargets after the dwell times of 1 minute, 5 minutes, 10 minutes, 30minutes, 1 hour, 12 hours, 24 hours, 2, days, 5 days, and 7 days. After7 days of dwell time, all solutions were treated with light again for 1minute, and a target was treated after 1 minute of dwell time. Theresults are summarized in Table 1.

TABLE 1 Time after solution 3% H₂O₂ 0.3% H₂O₂ 3% H₂O₂ with iron 0.3%H₂O₂ with iron exposed % % % % Control to light CFU Reduction CFUReduction CFU Reduction CFU Reduction CFU per prior to per vs. per vs.per vs. per vs. Time carrier application carrier Control carrier Controlcarrier Control carrier Control 0 6.04E+05 0 N/A N/A N/A N/A N/A N/A N/AN/A 1 min 7.00E+04 88.42% 1.10E+04 98.18% 3.80E+04 93.71% 1.41E+0576.67% 5 min 7.00E+04 88.42% 3.00E+04 95.04% 4.00E+04 93.38% 5.38E+0491.10% 10 min 3.10E+04 94.87% 1.98E+05 67.24% 8.50E+04 85.93% 2.13E+0464.75% 30 min 2.80E+04 95.37% 7.00E+04 88.42% 7.10E+04 88.25% 6.88E+0488.62% 1 hr 7.10E+04 88.25% 7.00E+04 88.42% 7.00E+04 88.42% 9.10E+0484.94% 12 hr 9.20E+04 12 hr 1.80E+04 80.43% 1.27E+05 nr 8.10E+04 11.96%1.10E+05 nr 24 hr 1.33E+05 24 hr 2.10E+04 84.21% 1.40E+04 89.47%1.60E+04 87.97% 1.55E+05 nr 2 days 3.00E+05 2 days 9.00E+04 70.00%2.64E+05 12.00% 8.70E+04 71.00% 3.39E+05 nr 5 days 4.50E+04 5 days3.29E+03 92.69% 4.40E+04 2.22% 1.60E+04 64.44% 2.43E+03 94.60% 7 days9.80E+04 7 days 1.50E+04 84.69% 7.70E+04 21.43% 2.07E+05 nr 7.10E+0427.55% 7 days* 1.00E+04 89.80% 1.03E+05 nr 3.00E+04 69.39% 2.30E+0476.53% *= reactivation with light of 400 to 420 nm for 1 minute; nr = noreduction

EQUIVALENTS

The foregoing description and accompanying figures illustrate theprinciples, exemplary embodiments, and modes of operation of theinvention. However, the invention should not be construed as beinglimited to the particular exemplary embodiments discussed above.Additional variations of the exemplary embodiments discussed above willbe appreciated by those skilled in the art. Using no more than routineexperimentation, one skilled in the art will recognize or be able toascertain, many equivalents to the specific embodiments and methodsdescribed herein. Such equivalents are intended to be encompassed by thescope of the following claims.

Therefore, the above-described exemplary embodiments should be regardedas illustrative rather than restrictive. Accordingly, it should beappreciated that variations to those exemplary embodiments can be madeby those skilled in the art without departing from the scope of theinvention as defined by the following claims. For example, the relativequantities of the ingredients may be varied to optimize the desiredeffects, additional ingredients may be added, and/or similar ingredientsmay be substituted for one or more of the ingredients described.Additional advantageous features and functionalities associated with themethods, combinations and devices of the present disclosure will beapparent from the appended claims.

1. A system for reducing microbial, and/or mineral, and/or chemicalconcentration in a substance, and/or for reducing biofilms formed in thesubstance, on the surface of the substance, or on the surface ofequipment involved in the storage, transport or processing of thesubstance, comprising: an oxidizing agent introducing device forintroducing an effective amount of a composition comprising an oxidizingagent compound into the substance to be treated; and at least oneradiation emitting device for exposing the composition comprising theoxidizing agent compound to radiation of certain wavelengths for periodsof time ranging from less than 1 second to days, wherein the radiationemitted by the at least one radiation emitting device is selected fromthe group consisting of particle radiation, acoustic radiation, andelectromagnetic radiation selected from the group consisting ofultraviolet light, visible light, x-rays, and gamma (γ) radiation,wherein the system is adapted for use in a reaction container forprocessing the substance to be treated, and the at least one radiationemitting device is a radiation emitter which has a specific gravity forallowing the radiation emitter to rest in the reaction container forprocessing the substance to be treated at a location where microbes,minerals, and chemicals are concentrated; or wherein the system isadapted to use in a pipeline in which the substance to be treated flows,and the at least one radiation emitting device is a lining layer forinside the pipeline for transporting the substance to be treated; andwherein the composition comprising the oxidizing agent compoundfunctions together with the radiation of certain wavelengths to providea synergistic reaction creating increased quantities of ElectronicallyModified Oxygen Derivatives (EMODs) that also exhibit increased times ofeffectiveness relating to antimicrobial properties, biofilm reducingproperties, and mineral and chemical and corrosion reducing propertieswhen compared and contrasted to EMODs that are not subject to thedescribed synergistic reaction.
 2. The system of claim 1, wherein thesubstance to be treated is crude oil, gas, hydrocarbons, water,wastewater, frack water, food, produce, animals, production fluids,soil, or air.
 3. The system of claim 1, wherein the system is adaptedfor use in the reaction container for processing the substance to betreated, wherein the at least one radiation emitting device is theradiation emitter which has the specific gravity for allowing theradiation emitter to rest in the location of the reaction containerwhere the microbes, minerals, and chemicals are concentrated, andwherein the oxidizing agent compound introducing device is a pump forintroducing the oxidizing agent into the reaction container.
 4. Thesystem of claim 1, wherein the system is adapted to use in the pipelinein which the substance to be treated flows, wherein the oxidizing agentcompound introducing device is positioned at one of: a location,relative to a direction that the substance flows in the pipeline, thatis upstream of the at least one radiation emitting device so that theoxidizing agent compound is exposed to radiation emitted from the atleast one radiation emitting device after being introduced into thepipeline, a location at which the oxidizing agent is dispensed into thesubstance while the oxidizing agent compound is being exposed to theradiation emitted from the at least one radiation emitting device, or alocation at which the oxidizing agent compound is exposed to radiationemitted from the at least one radiation emitting device before theoxidizing agent compound is introduced to the pipeline, and wherein thesystem is configured so that after the location in the pipeline in whichthe oxidizing agent compound is exposed to radiation, the treatedsubstance continues flowing further downstream in the pipeline. 5.(canceled)
 6. The system of claim 1, wherein the system is adapted toexpose the oxidizing agent compound to a radiation of a certainwavelength from the at least one radiation emitting device to create asynergistic reaction while the oxidizing agent introducing deviceintroduces the oxidizing agent compound to the substance.
 7. The systemof claim 1, wherein the system is adapted to expose the oxidizing agentcompound to a radiation of a certain wavelength from the at least oneradiation emitting device to create a synergistic reaction after theoxidizing agent introducing device introduces the oxidizing agentcompound to a substance.
 8. The system of claim 1, wherein the radiationemitting device is configured to emit radiation of certain wavelengthsbetween 200 nanometers and 600 nanometers.
 9. The system of claim 1,wherein the effective amount of the composition provides a minimalamount of the oxidizing agent compound to result in a measurable ordetectable effect on the microbial concentration, mineral concentration,chemical concentration and/or the biofilm formation.
 10. The system ofclaim 1, wherein the effective amount of the composition provides aconcentration of the oxidizing agent compound that is between 0.001percent to 100 or greater percent of the volume of the substance to betreated.
 11. The system of claim 1, wherein the effective amount of thecomposition comprising the oxidizing agent compound is determined on thebasis of any one or more of the density, pH, temperature, viscosity andlight absorbing quality of the substance to be treated, and size andshape of a container thereof.
 12. The system of claim 1, wherein theoxidizing agent compound is hydrogen peroxide, urea, carbamide peroxide,peracetic acid, hypochlorous acid, chlorine, or benzoyl peroxide. 13.The system of claim 1, wherein the system is adapted for use in thereaction container for processing the substance to be treated, whereinthe at least one radiation emitting device is the radiation emitterwhich has the specific gravity allowing the radiation emitter to rest inthe location of the reaction container for the substance where themicrobes, minerals, and chemicals are concentrated, and wherein theoxidizing agent introducing device is a titration system introducing theoxidizing agent compound to the reaction container for the substance.14. The system of claim 1, wherein the at least one radiation emittingdevice is configured to apply the radiation of certain wavelengths tothe oxidizing agent more than once.
 15. (canceled)
 16. The system ofclaim 1, wherein the composition comprising the oxidizing agent compoundis administered into the pipeline.